Pyrazole derivatives



United States Patent 3,309,379 PYRAZOLE DERIVATIVES Tomoyoshi Toyosato,Kyoto, Michihiko Ochiai, Suita, Hiroshi Hagimoto and Hiroshi Tamura,Kyoto, and Toshiya Kamikado, Suita, Japan, assignors to Takeda ChemicalIndustries, Ltd., Osaka, Japan No Drawing. Filed Aug. 9, 1963, Ser. No.301,201 Claims priority, application Japan, Aug. 10, 1962, 37/ 34,645 16Claims. (Cl. 260-310) The present invention relates to novelpyrazole'derivatives and to their use for agricultural purposes. Moreparticularly, the pyrazole derivatives are those of the formula N HsC Xaanac ripening, flower-production and dormancy or, in the case ofcertain Weeds, have a withering action,

There have been reported many kinds ofplant growth regulators, but onlya few of them are actually utilized for agricultural purposes, becausemost of them can not be used without risk of harm to desired culturalplants, or the agents are effective only to the non-intact plant, forexample, to stem section, leaf disk or callus tissue, or a large amountof the agents is required, or the agents can not be applied to plantsbefore rain or in rain.

Although many attempts have been made to overcome the aforesaidshortcomings and other disadvantages, none, as far as the presentinventors are aware, has been entirely successful when applied topractical use.

The present invention provides a series of new pyrazole derivatives ofthe above-mentioned Formula I, having a remarkable plant growthregulating activity upon application of a small quantity of compound toplants, with no discernible change in activity even in the case of rainjust after an application to plants.

It is an object of the present invention to provide plant growthregulators which are free from the above-mentioned shortcomings ordisadvantages. Another object is to provide new pyrazole derivatives.

The present invention also contemplates providing methods forpreparation of the said pyrazole derivatives. Among the further objectsof the present invention is the provision of plant growth regulatorswhich contain the pyrazole derivatives (1), and their use in regulatingplant growth.

Other objects and advantages will become apparent from the followingdescription taken in conjunction with the examples.

The pyrazole derivatives (I) of this invention can be 3,309,379 PatentedMar. 14, 1967 "ice synthesized through the reaction shown in thefollowing reaction formulae:

6) (3H3 Xu H i HQO \N/ Y (u) Xu HC=COH3 I-IlTI-NH:

B OR4 CO-A-O In the above-mentioned formulae, Y stands for a halogen,advantageously Cl, R stands for H or lower alkyl, B stands for an acyl,a cyano, or an alkoxycarbonyl group, and X, n and A have the samesignificance as those in the Formula 1, respectively.

The alkyl group represented by R or X in the foregoing formulae, islower alkyl and may, for example, be methyl, ethyl, propyl, isopropyl,butyl or the like. As the halogen represented by X or Y there may bechlorine or bromine. The alkyl group as the constituent of thealkoxycarbonyl group represented by B, the alkyl group as theconstituent of the alkoxy group represented by X, and the alkyl group asthe constituent of hydroxyalkyl or alkoxyalkyl represented by X in theformulae are likewise lower alkyl (of. first sentence of the presentparagraph).

In case the number n is greater than 1, each X may be the same as ordifferent from every other X.

Among the acyl groups represented by X or B in the above formulae, theremay, for example, be included the formyl, acetyl and benzoyl groups.

The alkylene group represented by A may be a straight or branched chain;for example, it may be methylene, ethylene, trimethylene,tetramethylene, pentamethylene, ethylidene, l-methylethy-lene,Z-methylethylene, l-methylpropylene, or 2-ethylethylene.

As previously described, the pyrazole derivatives of the presentinvention may be provided by the reactions as shown in theabove-mentioned reaction formulae (i) or (ii).

The reaction (i) may be carried out in the presence or absence of asuitable solvent. As solvent, there may be used such organic bases aspyridine, triethylamine, dimethylaniline or the usual organic solventssuch as acetone, methylethylketone, dimethylformamide, etc. The reactionis generally effected at room temperature (15 to 30 (3.), and it may becontrolled by heating or cooling, if necessary.

The reaction (ii) may be carried out in a suitable solvent. The solventmay, for example, be water, methanol, ethanol, acetic acid, benzene,etc., or a mixture consisting of two or more of these solvents. Thereaction may be promoted by the -addition of a small amount of acid tothe reaction system. The reaction may be effected at room temperature,and may also be controlled by heating or cooling, if necessary.

The following list sets forth a wide variety of pyrazole derivativesprepared by the method of the present invention, which are useful asplant growth regulators according to the present invention.

(1 1-(2,3,6-trichlorophenoxyacetyl)-3-5-dimethylpyrazole (2)1-(3-methoxyphenoxyacetyl)-3,5-dimethylpyrazole (3)1-(2,3,4,5-tetrachlorophenoxyacetyl) -3,5-dimethylpyrazole (4)1-(2-formyl-4-chlorophenoxyacetyl)-3,5-dimethylpyrazole1-(Z-formyl-4-chlorophenoxyethyloxacetyl) -3,5-

dimethylpyrazole (6) l- 2-chlorophenoxyacetyl) -3,5 -dimethy1pyrazole(7) 1- 2-ethoxyphenoxyacetyl -3 ,5 -dimethylpyrazole.

In practice, and to realize the desired activity, the plant growthregulators of the present invention are advantageously applied to plantsin the form of the compositions such as dust, emulsion, suspension orsolution. In other words, the plant growth regulator compositions of thepresent invention comprise essentially at least one active compound(pyrazole derivative) represented by the above-mentioned Formula Itogether with a suitable carrier (e.g. extender and/or conditioningagent) of the type commonly employed for the carriers of a known growthcontrol agent. It is not intended, in this respect, that the presentinvention be limited to any specific proportions of activeingredients(s) (I) and adjuvant.

The compositions may be readily prepared ab initio or may be egg. in theform of concentrates comprising active ingredient ('I) with only a minoramount of an adjuvant, eg a surface active agent. Such a concentrate iseconomical as regards transportation, storage and the like, and mayeasily be admixedprior to usewith additional adjuvant to give thedesired concentration of the active ingredient when it is applied. Theadjuvant may be selected depending on plants to be treated, propertiesof active ingredient and other adjuvant to be used together, andconditions of use.

Thus, if both the active ingredient and adjuvant(s) are water-soluble,the composition may be applied in the form of an aqueous spray. If, forexample, a water insoluble adjuvant is employed-e.g. if the compositioncomprises a water-insoluble adjuvant-the composition may be applied asan aqueous dispersion. It is also possible e.g. merely to mix the activeagent, in powder form, with a powdery adjuvant and to use the mixture(dust). Or, the powder mixture may be suspended in water or in an oil,such as gasoline, kerosene, etc. which,

upon mixing with water, forms eg an oil-in-water emulsion containing theactive ingredient. When the compositions are used in dust form, theadjuvant (or diluent) may be e.g. talc, clay, diatom-aceous earth, lime,calcium sulfate, kaoline and the like.

When the compositions are used in the form of liquid, the adjuvant(diluent) is eg water, an aqueous solvent, a volatile or non-volatileorganic solvent, e.g. an alcohol such as methanol, ethanol, etc., aketone such as acetone, methylethylketone, etc., an ether such asdioxane, tetrahydrofuran, etc., an aromatic hydrocarbon such as benzene,toluene, xylene, etc., a halogenated hydrocarbon such as chloroform,carbon tetrachloride, etc., an ester such as ethyl acetate and oil,etc., the compositionas afore-indicated-taking the form of a solution,emulsion or suspension depending on the nature of the materialsemployed.

The new plant growth regulating compositions may further contain wettingagents, dispersing agents and emulsifiers such as suitable surfaceactive agents e.g. polyoxyethyleneglycolethers,polyoxyethyleneglycolesters, polyoxyethylene derivatives of sorbitanmonolaurate (monooleate, monostearate), polyoxyethylenealkylarylether,alkyl sulfonate, alkylaryl sulfonate, alkyl sulfosuccinate, etc. Theymay also contain adherent or sticking agents, and also otheragricultural chemicals, e.g. pesticides, fungicides, manure orfertilizer growth controlling agents, plant hormone, etc., all thesematerials being considered adjuvants.

It is within the scope of the present invention to employ otheradjuvants than those hereinbefore mentionede.g. solid or liquiddiluents, emulsifiers, dispersants, surface active agents orotherwise-those already mentioned being merely illustrative.

The essence of the present invention does not reside in any specificadjuvant but in a composition consisting essentially of at least onecompound of the Formula I and an appropriate inert agricultural adjuvantwhich does not prejudice the activity of the composition.

Generally speaking, an effective amount for plant growth regulation issatisfied with the following quantitative relationships.

A dust or oil composition for direct application to plants may containfrom 0.00001 percent to 10 percent or more of the active ingredient(s)by weight. When the composition is prepared for actual use in the formof sprays or more dilute dusts, the content of the active ingredient(s)may vary from about 0.01 percent to as high as 0.1 percent by weight,the balance of the composition being one of the diluents and/or surfaceactive agents (adjuvants) previously mentioned.

Content of the active ingredient in an aqueous dispersion may similarlyvary from a very low percentage, e.g. 1 percent by weight, where thedispersion is applied directly to plants, to a relatively highpercentage, tag. percent by weight, where the dispersion is employed asa concentrate, the balance in each case being constituted by an adjuvantor adjuvants.

The plant growth regulators of the present invention promoteleaf-expansion, shoot-elongation, root-initiation, fruit-set,fruit-development, fruit ripening, flower-production or break dormancyof plant (bud or seed), or induce parthenocarpy, or inhibitabsciss-layer formation at a considerable low concentration and inhibitgrowth or kill weeds at a considerable high concentration.

Among these uses of the present plant growth regulators effects on theregulation of fruit-development, i.e. effects on inducing parthenocarpy,inhibition of absciss layer formation, fruit-drop prevention,stimulation of fruit-development, stimulation of fruit-ripening, andelfect on suppressing or withering weeds are very prominent.

Heretofore, p-chlorophenoxy acetic acid, fl-naphthoxy acetic acid,2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxypropionic acid,a-naphthaleneacetic acid or a mixture of two or three of these have beenput to use for fruit-drop prevention or fruit-set stimulation, expectingtheir hormonal effect. These known compounds, however, are not free fromthe shortcomings that a large amount of the agents must be applied, orthat the agents may do auxonic (hormonal) injury to plants to which theyare applied.

The plant growth regulators of the present invention, on the other hand,display a superior hormonal efiect on plants in spite of the applicationof a lesser amount in comparison with the above-mentioned compounds ortheir mixtures.

In application of the plant growth regulator of the present invention toplants for the purpose of growth promotion of the plants, it can beapplied or sprayed onto seeds, roots, sprouts, stems, leaves, flowers,flower clusters, fruits, etc., in a suitable concentration for thepurposes.

In application of the plant growth regulator of the present invention toplants for the purpose of growth inhibition of the plants or weeds, itcan be applied to soil in pre-emergence of the plants or inpost-emergence in a suitable concentration for the purpose.

In the treatment of paddy field weeds, the plant growth regulator maydirectly be applied to the plants or in paddy field where the plantsgrow. The plant growth regulator of the present invention can causecontact and auxonic (hormonal) injury, growth inhibition or wither-- ingof weeds by direct or indirect contact therewith, and moreover, theplant growth regulator displays inter-genusselectivity among gramineousplants.

Examples of regulative effect upon plant growth by application of thepyrazole derivativies (I) are set forth as follows:

EXAMPLE A Growth promotion test Growth-promoting and inhibiting actionof the present compounds were tested by the Avena straight growth 6method. Ten pieces of 5 millimeter length of subapical applied to 20pots, respectively. This is applicable section of Avena coleoptiles weresoaked in the solution to the same term used in all other examples.) for24 hours at 25 C. in the dark and their lengths were Method: Respectiveaqueous solutions each containmeasured under the travellingmicroscope.ing one of the following six compounds in various In the table, thecompounds are represented by the cor- 5 concentration are applied to theflowers with a responding numbers shown below; brush, and days requiredfor ripening and the features of fruit-set and fruit-development werel-(2,4-dichlorophenoxyacetyl)-3,5-dimethyl- 7 Observed- Pyrazole I (2)Results- In the following two tables, the compounds1-(4-chlorophenoxyacetyl)-3,5-d1methylpyrazole II are represented by thecorresponding numbers shownl-(2,4,5-trichlorophenoxyacetyl)-3,5-d1methylb l Pyrazole 1H 1 2 4dichloro henox met 1 i 1- 1-[u-(2,4-dichlorophenoxy)propionyl]-3,5-dimethylg p y y d methy I Pl 3216 IV1-(4-ch1orophenoxyacetyl)-3,S-dimethylpyrazgle II 1-( y y y p yy 1 (2-.formyl -.4 chlorophenoxyacetyl) 3,5 dimethylpyrazole V methylpyrazoleIII TABLE I Fruit-development (millimeter) Average weight of Days re-Compounds Cone, Percentage Mean value Mean value treated fruit quiredfor ppm. of fruit-set of diameter of diameter in the ripening of fruits14 of fruit in harvest time days after the harvest (grams) theapplicatime tion Control (water) 0 48.3 27 x 27 54 x 43 128.2 40.3 I 177. 2 31 x 31 53 x 48 137.4 36.5 10 96.1 39 x 36 67 x 51 145.6 32.3 87.7x 35 65 x 51 140.9 33.1 40 85.4 37 x 31 64 x 51 140. 2 33.4 II 1 53.7 27x 27 54 x 43 127. 7 39. 2 10 57. 6 30 x 23 54 x 45 129.1 37.1 20 59. 332 x 31 54 x 46 123.9 37.1 40 60.1 33 x 30 56 x 49 132. 5 35.9

1 Cone. means concentration. 2 P.p.m. means parts per million.

' TABLE II Fruit-development (average Compounds Cone, Percentage ofweight of Days required p.p.m. fruit-set treated fruit for ripening inthe harvest time) (gram) 1 Cone. means concentration. a P.p.m. meansparts per million. TABLE.MEAN VALUE OF TEN SECTIONS EXAMPLE (1 Fruit-setpromotion test (1) Conditions- 0 t not pm) 0 01 1 10 100 Tested plants:Eggplant (Solarium melongena).

omen m p 55 Test scale: One plant per one pot, 20 pots (%000 are Sectionlength (milliliter) Tested Compound, Wagners pot) per 1 plot, 2repetitions.

5.37 2.32 7 8; Method: The solutions of the following four com- 1 4 12 1pounds are applied to flowers and peduncles with a .5. 94 6. 0s 6. 2g2.1; brush (2) ResultIn the following table, the compounds are P m meansconcentrations in parts per million. represented by the correspondingnumbers o n below: EXAMPLE Bl-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole I Fairs andfruibdevelownem test 1-(4-chlorophenoxyacetyl)-3,5-d1methylpyrazole II(1) Tmato (Lyc pe o esculentum Compounds Concentration (p.p.m.Percentage of fruit-set Min) I 10 100 Test scale: 20 pots are Wagner spot) per 1 20 100 plot, one plant per one pot, 2 repetitions i8 1 (Theterm lot used in the following examples 11 0 00 means a definite treatedarea of experiment in which g 33 the preparation of this invention isapplied, in other I 4 100 Control (water) 66 words, for example, 20 potsl plot used in EX- ample B has such a meaning that the preparation ofthis invention having a certain concentration is means concenmuons PerEXAMPLE D Inhibition percentage Growth inhibition test of young stageplants Fresh weight at tre P Fresh weight at non-treated plot) X 100((1) Conditions 5 Tested plants: Rice (Oryza sativa L), cucumberW1ther1ngpereentage= (Cucumis sativus L.) and cocksfoot (Panlcum Numberf completely withered plant crusgalli Number of used test plant Testscale: seeds per one plot, 3 repet1t1ons.

Method: Germinating seeds of equal state of germ- Result-Using P Y Yination are placed in a petri dish (diameter: 9 cm.) 10dimethylpyrazole, 1s shown below:

Plants Rice Soybeans Tomato Buckwheat Concentra- Inhibition witheringInhibition Withering Inhibition Wlthering Inhibition withering Compounds'tion (percent) (percent) (percent) (percent) (percent) (percent)(percent) (percent) (percent) 5 Concentrations in the present exampleare shown by on which filter paper is spread and respective 5weight-percentage.

cubic centimeters of the suspensions of each con- EXAMPLE F taining oneof the following compounds are poured. Then they are incubated at C. inthe dark. Growth al y? w'thermg test by an (2) Result-Five days aftertreatment, root length and app [Ca 0 a pre'emergence stem length arerespectively measured to calculate inhibi- (1) Conditionstionpercentages. Tested plants: Rice, soybean, buckwheat and tomato.

Plant Rice Cucumber Cocksfoot (On 2a sativa L.) (Cucumis sativus L.)(Panicum crusgallz' L.)

Root Stern Root Stem Root Stem length length length length length lengthInhibition Percentagez 1-(4-ehlorophenoxyacetyl)- 3,5-dimethylpyrazole:

p.p.m. 95 5 90 0 V 90 62 10 p.p.1n. 95 0 100 20 93 91 100 p.p.m. 93 0100 38 93 93 1-(2, 4-dichl0r0phen0x acetyl)-3, 5-dimethyl- EXAMPLE ETest scale: 1 pot are Wagners pot) per 1 plot,

about 10 plants per pot, 2 repetitions. i 60 Method: Respective 10 cubiccentimeters of the solu- Growth mhzbltwn an withering test by tions ofthe following compounds per one plot is spray method at post-emergenceapplied to soil at pro-emergence.

(2) ResultOne month after treatment, the result is (1) Conditionsexamined to calculate inhibition percentages and Wither- Test plants:Rice, Soybean (Glycine max Merrill), mg percentages. Inhibitionpercentages and withering buckwheat (Fagopyrum momentum Moench) andpercentages have the same meaning as those defined in tomato(Lycopersicon esculentum Mill). Example Test scale. 1 pot (1/5000 arewagneras pot) per 1 plot, In the follow ng table, the compounds arerepresented 10 Plants per one plot, 2 repetitions by the correspondingnumbers shown below.

Method: Respective 10 cubic centimeters of the 1 (4 chloro 2methylphenoxyacetyl) 3,5 diemulsions each containing one of thefollowing methylpyrazole I three compounds are sprayed at 3-4 leavesstage. 1 (2,4,5 trichlorophenoxyacetyl) 3,5 dimethyl- (2)Observation-Fourteen days after treatment, repyrazole II sults areexamined to calculate inhibition percentages and1-(4-chlorophenoxyacetyl)-3,5-dimethylpyrazole III witheringpercentages. 1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole IVPlants Rice Soybean Tomato Buckwheat Goncentra- Inhibition WitheringInhibition Withering Inhibition Withering Inhibition Withering Compoundson (percent) (percent) (percent) (percent) (percent) (percent) (percent)(percent) (percent) I 0.05 7.1 0 44.5 0 23.1 0 39.3 0 0.1 36.4 0 73.833.4 57.7 25.0 100 100 0.5 36.4 0 100 100 100 100 87.5 75 II 0.05 0 080.9 66.7 11.6 0 25.0 25.0

0.1 0 0 83.9 66.7 46.2 0 0 0 0.5 9.1 0 100 100 77.0 58.0 26.8 25.0 III0.1 0 0 100 100 100 100 76.0 60 0.5 0 0 100 100 100 100 86.8 60 1.0 40 0100 100 100 100 100 100 2.0 40 0 100 100 100 100 100 100 IV 0.1. 0 035.3 0 71.2 50 64.0 38 0.5 0 0 85.0 50 90.2 75 88.2 50 1.0 40 0 100 100100 100 100 100 2.0 80 100 100 100 100 100 100 Concentrations in thepresent example are shown by weight-percentage.

EXAMPLE G Example 4 Test for fruit-drop prevention A tablet comprising0.2 part of 1-(2,4,5-trichlorophenoxyacety1)-3,S-dimethylpyrazoletin96.9 parts of lactose, (l) Cond1t1oni i 10 parts of polyethylene glycol(5% methanol solution), Test E pp us pumlle M111 var. dulczsszma 1.2parts of starch and 1.2 parts of talc, according to the Koidz) Iinvention, is useful in promoting fruit-ripening. Method: Solutions ofvarious concentrations containing1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpy- E am I 5 razole areapplied to fruits and fruit-stalks about x p 8 one month before theharvest time, and the difference in the number of dropped fruits betweenA powder comprising 2 parts of 1-(4-chlorophenoxytreated trees andnon-treated ones is observed. acetyl)-3,5-dimethylpyrazole and 98 partsof talc, accord- (2) Result ing to the invention, is useful in promotingroot-initiation.

Concentration Number of Number 01' Percentage of (parts per treatedfruits dropped fruits dropped fruits (million) Treated 4. 9 30 9 30 9.730 3 10 19.4 30 7 23 38.8 30 8 27 Non-treated 30 11 37 For the purposeof giving those skilled in the art a bet- Example 6 5 lindgrstandmgpreserg i ggg ig g i g g A wetting powder comprising 20 parts ofl-(2,4-di- 1 us m We examp es 0 preset y p ehlorophenoxyacetyl) 3,5dimethylpyrazole, 4 parts of of preparations of pyrazole derivatives andof the compositions containing pyrazole derivatives. In these examples,parts-and percentages are by weight.

Example 1 An emulsion comprising 0.1 part of1-(4-chloropl1enoxyacetyl)-3,5-dimethylpyrazole, 0.3 part ofpolyoxyethylenesorbitane. monolaurate, 50 parts of acetone and 49.6parts of benzene, according to the invention, is useful in promotingfruit-set and fruit-ripening.

Example 2 A solution comprising 0.2 part of1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole, 0.8 part ofpolyoxyethylenealkylarylether and 99 parts of acetone, according to theinvention, is useful in promoting fruit-set and fruit development.

Example 3 sodium ligninsulfonate, 4 parts ofpolyoxyethylenealkylarylether and 72 parts of clay, according to theinvention, is useful in withering weeds.

Example 7 A granule comprising 2 parts of1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole and 98 parts ofbentonite, according to the invention, is useful in withering weeds.

The following examples set forth presently-preferred exemplaryembodiments of the preparation of compounds Example 8 To a mixture of 20parts of ethanol and 5 parts of water are added 2 parts of4-chlorophenoxyacethydrazide, 1 part of acetylacetone and 0.3 part of10% hydrochloric acid, and the mixture is refluxed for 2 hours. Aftercooling, the separated crystals are recrystallized from ethanol to give1-(4-chlorophenoxyacetyl)-3,5-dimethylpyrazole as colorless scalesmelting at 112-113 C. Yield 2 parts.

Analysis.-Caleula-ted: C, 58.98%; H, 4.95%; N, 10.58%. Found: C, 59.14%;H, 4.82%; N, 10.32%.

Example 9 To 30 parts of ethanol are added 2.3 parts of2,4-dich10rophenoxyacethydrazide, 1 part of acetylacetone, and

0.3 part of 10% hydrochloric acid, and the mixture is refluxed for 1.5hours. After cooling, the separated crystals are recrystalized fromethanol to give 1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole ascolorless needles 12 Analysis.Calculated: C, 48.75%; H, 3.78%; N.17.50%. Found: C, 48.91%; H, 3.94%; N, 17.57%.

Example 14 melting at 132-134 C. Yield 2.5 parts. To a solution of 1.5parts of 3,5-dimethylpyrazole in Analysis.Calculated: c, 52.19%; H,4.04%; N, 5 parts of py i op added 2,4-dichlorophe- 9 3 d; c, 51407 H,425%; N, 929%, noxyacetylchloride. After the mixture is stirred for 1hour, 40 parts of water are added. The separated crys- Example tals arerecrystallized from acetone-water to give 1-(2,4- To a mixture of 20parts of ethanol and 10 parts of 10dichlorophenoxyacetyl)-3,5-dimethylpyrazole as colorless water are added2 parts of 2-chlorophenoxyacethydrazide, needles melting at 132134 C.Yield 2.4 parts. 1 part of acetyla'cetone and 0.3 part of 10%hydrochloric Analysis.-Calculated: C, 52.19%; H, 4.04%; N, acid, and themixture is allowed to react at 50 C. for 6 9.3%. Found: C, 52.06%; H,4.01%; N, 9.63%. hours. After cooling, the separated crystals are re-Example crystallized from ethanol to give 1-(2-chlorophenoxyace- 15tyl)-3,5-dimethylpyrazole as colorless prisms melting at A miXtllfe 0fParts Of l PY and 3 124 126 C Yi ld 15 parts, parts of4-chlorophenoxyacetylchloride is heated at 100 Analysis.--Calculated: C,58.98%; H, 4.95 N, C. for 2 hours. After cooling, 40 parts of water isadded 10;53%, d; 59.95%; 499%; 10 43% to the reaction mixture. Theseparated crystals are re- E l 11 crystallized from acetone-water togive 1-(4-chloro phexamp e noxyacetyl)-3,5-dimethylpyrazole as colorlessscales To a mixture of 30 parts of ethanol, 5 parts of water and meltingat 112-113 C. Yield 2.8 parts. 0.2 part of 10% hydrochloric acid areadded 2.1 parts of Analysis.Calculated: C, 58.98%; H, 4.95%; N,4-chloro-2-methylphenoxyacethydrazide and 1 part of 10.58%. Found: C,59.14%; H, 4.82%; N, 10.32%. acetylacetone. The mixture is heated at 60C. for 3 hours. After cooling, the separated crystals are recrystal-Example- 16 lized from ethanol to give 1-(2-methyl-4-chlorophenoxy- T050 Parts Of ethanol containing 1 P Of 10%hydroacetyl)-3,5-dimethylpyrazole as colorless prisms melting at Chloricacid are added Parts Of y y 137 5 13 5 C, Yi ld 2 partschiorophenoxyacethydrazide and 1 part of acetylacetone. Analysiscalculatedj 3, 032 75,; H, 542%; The reaction mixture is heated at 50 C.for 1 hour. 10.05%. Found: C, 60.33%; H, 5.53%; N, 1() 32% Aftercooling, the separated solid is recrystallized from Exam [8 12dimethylformamide-ethanol to give I-(Z-hydroxymethylp4-chlorophenoxyacetyl)-3,5-dimethylpyrazole' as colorless To a mixtureof parts of ethanol, 5 parts of water needles melting at 133 C. Yield2.4 parts. and 03 part of 10% hydrochloric acid are added 2.7 parts 35Analysis.--Calculated: C, 57.06%; H, 5.14%; N, of2,4,5-trichlorophenoxyacethydrazide, 1 part of acetyl- 9.51%. Found: C,56.89%; H, 4.96%; N, 9.43%. acetone, and the mixture is refluxed for 1.5hours. After The following compounds can be synthesized in simicooling,the separated crystals are recrystallized from lar manner.

TABLE 2 l R j l R Remarks for Solvent for recrystallizationDMF=dimethylformamide.

R R R A Xn Melting point Solvent for reerystalli- Appearance of crystals0.) zation 3-01 100-101 Colorless risms. 2, 4-di-C1 108 Do. p 2, 5-di-C1112-113 D0. 2, fi-di-C 145 Do. 2-NO2 130-131 D0. 3-NOz 137137.5 D0.

4-N02 168-169 Do.

OH 2, 3, 4, fi-tetra-CL... 159-160 Colorless crystals.

CH 2, 3, 4, 5, G-penta-CL. 180-181 Do.

ethanol to give 1-(2,4,S-trichlorophenoxyacetyl)-3,5-dimethylpyrazole ascolorless prisms melting at l77-178 C. Yield 1.9 parts.

Analysis.-Calculated: C, 46.76%; H, 3.32%; N, 8.39%. Found: C, 46.74%;H, 3.35%; N, 8.37%.

Example 13 To a mixture of parts of ethanol, 10 parts of Water and 1part of 10% hydrochloric acid are added 2.6 parts of2,4-dinitrophenoxyacethydrazide and 1 part of acetylacetone, and themixture is heated at C. for 1 hour. After cooling, the separatedcrystals are recrystallized from ethanol to give1-(2,4-dinitrophenoxyacetyl)-3,5- dimethylpyrazole as pale yellowishprisms melting at 161162 C. Yield 2 parts.

1. 1- 2-chlorophenoxyacetyl -3,5-dimethylpyrazole.

2. 1- 3-chlorophenoxyacetyl) -3-5-dimethylpyrazole.

3. 1- 4-chlorophenoxyacetyl) -3,5-dimethylpyrazole.

4. 1-(2 methyl-4-chlorophenoxyacetyl)-3,5-dimethylpyrazole.

5. 1 (2,4 dichlorophenoxyacetyl) 3,5 dimethylpyrazole.

6. 1 [a (2,4-dich1orophenoxy) propionyl] 3,5 dimethylpyrazole.

7. 1 (2,5 dichlorophenoxyacetyl) 3,5 dimethyl- 5 pyrazole.

8. 1 (2,6 dichlorophenoxyacetyl) 3,5 -'dimethy1- pyl azole.

9. 1 (2,4,5 trichlorophenoxyacetyl) 3,5 dimethylpyrazole. 1Q

10. 1-(2-nitrophenoxyacetyl)-3,5-dimethylpyrazole.

1 1. 1-(3-nitrophenoxyacety1) -3,5-dimethy1pyrazo1e.

12. 1-(4-nitrophenoxyacety1) -3,5-dimethylpyrazole.

13. 1-(2,4-dinitrophenoxyacety1)-3,5-dimethy1pyrazole.

14. 1-(2,3,4,6-tetrachlorophenoxyacetyl) 3,5-dimeth- 15 ylpyrazole.

15. 1 (2,3,4,5,6 pentachlorophenoxyacetyl)-3,5-dimethylpyrazole.

16. 1-(4 chloro 2 hydroxymethylphenoxyacetyl)- 3,5-dimethy1pyrazole.

References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCESRied et al.: Liebigs Annalen der Chemie, volume 626,

pages 98-103 relied on (1959).

Ried et al.: Liebigs Annalen der Chemie, volume 631,

pages 188 and 191-193 relied on (1960).

JOHN D. RANDOLPH, Primary Examiner.

WALTER A. MODANCE, Examiner.

20 N. S. RIZZO, N. TROUSOF, Assistant Examiners.

1. 1-(2-CHLOROPHENOXYACETYL)-3,5-DIMETHYLPYRAZOLE.
 4. 1-(2 -METHYL-4-CHLOROPHENOXYACETYL)-3,5-DIMETHYLPYRAZOLE.
 6. 1 -(A-(2,4-DICHLOROPHENOXY)PROPIONYL) -3,5 - DIMETHYLPYRAZOLE. 12.1-(4-NITROPHENOXYACETYL)-3,5-DIMETHYLPYRAZOLE.
 15. 1 - (2,3,4,5,6 -PENTACHLOROPHENOXYACETYL)-3,5-DIMETHYLPYRAZOLE.